JP2001316419A - Polymer compound, radically copolymerized resin composition, molding material, and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which can essentially improve the compatibility between a radically copolymerized unsaturated resin and a shrinkage depressing agent containing mainly polystyrene. SOLUTION: The radically copolymerized unsaturated resin composition comprises a radically copolymerized unsaturated resin and a polymerizing unsaturated monomer, containing a polymer material which is derived from a polymer compound as the precursor and has a function to make the unsaturated resin compatible with a compound added chiefly to depress the shrinkage, wherein the polymer compound is a product obtained by reacting a styrene polymer (A) containing mainly polystyrene and having one or more functional groups in the molecule with a compound (B) having two or more functional groups in the molecule at least one of which is reactable with the functional group of the styrene polymer (A), the polymer compound having at least one intact functional group originated from the compound (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radical copolymerizable polymer (d) for compatibilizing a radical copolymerizable unsaturated resin (a) with a compound to be added mainly for the purpose of reducing shrinkage. The present invention relates to a novel polymer compound (c) which can be produced by reacting with a reactive resin (a), a radical copolymerizable resin composition thereof, a production method thereof, a molding material, and a molded article. More specifically, the compatibility between the radical copolymerizable unsaturated resin (a) and the compound (b) to be added mainly for the purpose of reducing shrinkage is improved. Another object of the present invention is to provide a polymer compound (c) which is a precursor for producing a polymer substance (d) capable of solving the above problems. Further, the present invention provides a means for making the low-shrinkable unsaturated resin composition mixture one-packaged by the presence of the polymer substance (d), thereby increasing the added value of the molding material and the molded article.

[0002]

2. Description of the Related Art A radical copolymerizable unsaturated resin is mixed with a polymerizable unsaturated monomer and is suitably used as a raw material resin of a molding material as a liquid resin. However, the molding material using the radical copolymerizable unsaturated resin composition has a serious problem that the volume shrinkage occurring at the time of curing causes the molded product to warp or crack. For the purpose of improving this problem, various thermoplastic resins, for example, resins such as polystyrene, styrene-butadiene rubber, thermoplastic acrylic polymer, vinyl acetate, and saturated polyester have been used as low-shrinkage agents. However, these low-shrinkage agents have low compatibility with the radical copolymerizable unsaturated resin, have poor separation stability of the resin mixture, and separation after mixing has been inevitable. Further, in a molded article obtained from this resin mixture, separation of the low-shrinkage agent causes various molding defects such as scumming and color unevenness. As a matter of course,
It was difficult to store the resin mixture in a one-liquid state.

Therefore, a method of adding a compatibilizer as a third component has been studied. For example, US Pat.
No. 00 discloses an example in which a styrene-ethylene oxide block copolymer obtained by a living anion polymerization method is used as a compatibilizer. This compatibilizer has a high compatibilizing effect with respect to some radical copolymerizable unsaturated resins, and can maintain a stable dispersion state for a long period of time. Production was difficult.

On the other hand, a method of improving the compatibility by using an addition polymer in which a vinyl acetate block, an unsaturated polyester block, or the like is introduced as a low-shrinking agent is disclosed in, for example, Japanese Patent Publication No.
174424 and JP-A-11-92646. Although these improved type low-shrinking agents have the effect of delaying the time until separation, they have essentially not improved the compatibility and obtained a stable dispersion state.

[0005]

An object of the present invention is to provide a radical copolymerizable unsaturated resin composition comprising a radical copolymerizable unsaturated resin (a) and a polymerizable unsaturated monomer (a '). The radical copolymerizable unsaturated resin (a) is essentially improved in compatibility with the polymer to be added mainly for the purpose of reducing shrinkage at the time of curing, and can be dispersed in a resin mixed liquid state for a long period of time. A new polymer that can be produced by reacting a polymer substance (d) with a radical copolymerizable unsaturated resin, which can indicate the state or can improve molding defects during molding due to separation It is to provide a compound (c), a radical copolymerizable unsaturated resin composition, a molding material, and a molded article. More specifically, it improves the compatibility between a radical copolymerizable unsaturated resin and a compound to be added mainly for the purpose of reducing shrinkage, and solves storage and molding problems caused by poor compatibility. It is an object of the present invention to provide a precursor polymer compound (c) which can provide a compatibility-improving polymer substance (d). Further, by containing the polymer substance (d), a precursor polymer compound that enables the radical copolymerizable unsaturated resin composition to be made into one liquid, thereby enabling a molded article obtained to have high added value (C)
It is to provide.

[0006]

Means for Solving the Problems The present inventors have made intensive studies on these problems and as a result have completed the present invention.

That is, the present invention relates to a radical copolymerizable unsaturated resin composition comprising a radical copolymerizable unsaturated resin (a) and a polymerizable unsaturated monomer (a '). ) And a compound (c), which is a precursor for producing a polymer substance (d) having an action of making the compound (b) added for the purpose of lowering shrinkage compatible,
The polymer compound (C) comprises (A) a styrene-based polymer having polystyrene as a main component and one or more functional groups in the molecule, (B) two or more functional groups in the molecule, and At least one of the functional groups is reacted with a compound having a functional group capable of reacting with the functional group of the styrenic polymer (A), and the polymer compound (c) is derived from the compound (B). (C), preferably a styrene-based polymer (A), wherein at least one of the functional groups is a hydroxyl group, a carboxyl group, an epoxy group, an amino group, and a mercapto group. At least one functional group selected from the group, preferably at least one of the functional groups of the styrenic polymer (A) is located at a molecular terminal of the polymer, preferably a styrenic polymer (A ) Functional group But it is 1-4, preferably a number average molecular weight of the styrene polymer (A) is 100
0 to 50,000, preferably compound (B)
Is an organic polyisocyanate compound, preferably the polymer compound (C) is mainly composed of the polymer (A)
A compound having the structure of (A)-(B) when there is one functional group of
When the polymer (A) has two functional groups (B)-(A)-
It is a compound having the structure of (B), preferably having an average number of functional groups derived from the compound (B) of 1 to 4 remaining per molecule of the polymer compound (c), and preferably having a compound in the molecule. (B) a radical copolymerizable unsaturated resin having a functional group capable of reacting with the functional group of (A), a radical copolymerizable unsaturated resin composition comprising a polymerizable unsaturated monomer (A ′), The polymer obtained by adding the polymer compound (c) and reacting the radical copolymerizable unsaturated resin (a) with the polymer compound (c) in the radical copolymerizable unsaturated resin composition A radical copolymerizable unsaturated resin composition containing the substance (d). Preferably, after adding the polymerizable unsaturated monomer (a ') during or after the synthesis of the radical copolymerizable unsaturated resin (a) or after the synthesis of the radical copolymerizable unsaturated resin (a). A method for producing a radical copolymerizable resin composition characterized by adding and reacting a polymer compound (c), a molding material containing the radical copolymerizable resin composition, and the radical copolymerization It is intended to provide a molded article characterized by using the conductive resin composition or the molding material.

Next, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The styrenic polymer (A) having polystyrene as a main component and having at least one functional group in the molecule is a styrene-based polymer (A) having at least one functional group and having styrene as a main component. The synthesis method, structure, and the like are not particularly limited as long as the polymer described above is used. For example, a polystyrene polymer compound having a functional group at the terminal can be synthesized by a method such as radical polymerization using an azo-based initiator or living anion polymerization, and a polystyrene polymer compound having a functional group in a molecule is styrene. It can be synthesized by copolymerization with a functional group-containing unsaturated monomer. Further, a polymer obtained by epoxidizing an unsaturated bond portion in a styrene-conjugated diene block copolymer may also be used.

The constituent ratio of styrene in the styrene polymer (A) is preferably at least 50% by weight, more preferably at least 70% by weight. If the proportion of styrene is small, the compatibilizing effect later will be reduced.

The functional group of the styrene polymer (A) is preferably at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group, an amino group and a mercapto group. In addition, it is preferable that at least one of these functional groups is located at a molecular terminal of the polymer. The average number of functional groups per molecule of the styrene-based polymer (A) is not particularly limited. Preferred number of functional groups is 1 to 10,
More preferably, it is 1-4.

The number average molecular weight of the styrene polymer (A) is preferably 500 or more, more preferably 10 or more.
00 to 50,000. If the molecular weight is too small or too large, a sufficient compatibilizing effect cannot be obtained. In addition, the number average molecular weight of the present invention is measured by gel permeation chromatography.

The molecule of the present invention has two or more functional groups in the molecule,
The compound (B) in which at least one of the functional groups is capable of reacting with the functional group of the styrene-based polymer (A) is not particularly limited, and examples thereof include an organic polyisocyanate compound and a dicarboxylic acid. They are selected from chloride compounds, polyamine compounds, phosgene, carbonate compounds, thiophosgene, bischloroformate compounds and the like. Among these, an organic polyisocyanate compound is particularly preferably used in consideration of reaction operation and cost. The number of the functional groups is preferably 2.

The organic polyisocyanate compound includes, for example, 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene diisocyanate,
4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, naphthalene diisocyanate,
1,4-cyclohexane diisocyanate, 4,4'-
Dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate and the like are used. When control of the reaction is considered, tolylene diisocyanate and isophorone diisocyanate are preferably used.

The reaction for synthesizing the high molecular compound (C) from the styrene polymer (A) and the compound (B) may be carried out in a solvent or without using a solvent. From a viewpoint of a solvent. As the solvent,
Any material may be used as long as all of (A), (B) and (C) are soluble and do not react with the functional groups of (A) and (B). For example, polymerizable unsaturated monomers such as styrene, α-methylstyrene, vinyltoluene, and chlorostyrene, and organic solvents such as benzene, toluene, and xylene are exemplified. However, when an aromatic vinyl monomer is used as the polymerizable unsaturated monomer, conditions for the subsequent reaction with the radical copolymerizable unsaturated resin (a) are appropriately selected, and the conditions will be described later as necessary. Need to be added. When storing the polymer compound (c), it is preferable to replace the inside of the storage container with dry air or dry nitrogen gas.

In the polymer compound (C) of the present invention, one compound (B) is added to each one functional group of the polymer (A), and at least one functional group derived from the compound (B) is added. Preferably, it is of the remaining type.
Preferred examples of the structure include a polymer compound (C) having a structure of (A)-(B) when the polymer (A) has one functional group,
One or two functional groups derived from the compound (B),
When the polymer (A) has two functional groups (B)-(A)-
A polymer compound (C) having the structure of (B) and having one or two functional groups derived from the compound (B) is preferable. However, the polymer compound (c) of the present invention contains by-products. By-products include, for example, when (A) has one functional group, (A)-(B)-(A) and (A) have two functional groups.
(B)-(A)-(B)-(A)-(B)
And the like are given as examples. When the proportion of by-products increases, the radical copolymerizable resin (a) and the polymer compound (c)
The lower the proportion of by-products, the better, because the amount of the polymer substance (d) obtained by the reaction with the compound decreases and the compatibilizing effect decreases. When obtaining the polymer compound (c), it is important to select an appropriate reaction ratio between (A) and (B) and a reaction temperature in order to avoid generation of by-products. The reaction temperature is
Preferably it is 50-150 degreeC. The functional group of (A) is 1
In one case, the reaction ratio is preferably (A) :( B) = 1: 1
0.8 to 2. When (A) has two functional groups,
The reaction ratio is preferably (A) :( B) = 1: 1.6-4.

The number of functional groups derived from the compound (B) remaining per molecule of the main compound in the polymer compound (c) is preferably 1 to 4. More preferably, the number of residual functional groups is equal to the number of functional groups of the styrene-based polymer (A).

The synthesis reaction of the polymer compound (c) may be carried out in a solvent or without using a solvent, but is usually carried out in a solvent from the viewpoint of workability. As the solvent,
(A) (B) (c) Any components may be used as long as each component dissolves and does not react with a functional group in each component. However, when considering mixing with the radical copolymerizable unsaturated resin composition later, the same as the polymerizable unsaturated monomer (a ′) contained in the radical copolymerizable unsaturated resin composition is used. It is preferable to appropriately add a polymerization inhibitor described below.

A radical copolymerizable unsaturated resin composition having a functional group capable of reacting with the functional group of the compound (B) is defined as a radical copolymerizable unsaturated resin composition having a functional group capable of reacting with the functional group of the compound (B). It comprises a saturated resin (a) and a polymerizable unsaturated monomer (a ').

The radical copolymerizable unsaturated resin (A) having a functional group capable of reacting with the functional group of the compound (B) of the present invention includes, for example, unsaturated polyester resin, vinyl ester resin, vinyl urethane resin, acrylic Examples of the functional groups include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group.

The composition of the unsaturated polyester resin that can be used in the present invention is not particularly limited.
It is obtained from an unsaturated carboxylic acid or an α, β-unsaturated carboxylic acid, optionally containing a saturated carboxylic acid, and an alcohol. Since the unsaturated polyester (a) has a carboxyl group or a hydroxyl group at the molecular terminal, the polymer (c) can be reacted.

Examples of the α, β-unsaturated carboxylic acid include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, and dimethyl esters thereof.
These α, β-unsaturated carboxylic acids may be used alone or in combination of two or more.
As the saturated carboxylic acid, for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, head acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride,
Adipic acid, sebacic acid, azelaic acid and the like can be mentioned. These saturated carboxylic acids may be used alone or in combination of two or more.

On the other hand, examples of the alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 6-hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, glycerin monoallyl ether, hydrogenated bisphenol A, hydrogenated bisphenol A, ethylene oxide and propylene oxide adducts 2,2-bis (4-hydroxypropoxyphenyl) propane, 2,
Examples thereof include diols such as 2-bis (4-hydroxyethoxyphenyl) propane and 2-methylpropanediol, triols such as trimethylolpropane, and tetraols such as pentaerythritol. Each of these alcohols may be used alone or 2
A combination of more than one species may be used.

Further, dicyclopentadiene is added,
A dicyclopentadiene unsaturated polyester obtained by reacting with the above α, β-unsaturated carboxylic acid, saturated carboxylic acid and alcohol can also be used.

The unsaturated polyester resin (a)
Unsaturated polyester acrylate resin obtained by reacting glycidyl methacrylate with vinyl ester resin can also be used as vinyl ester resin.

The vinyl ester resin used in the present invention is a reaction product obtained by reacting an epoxy resin with an unsaturated monobasic acid. Since the vinyl ester resin has a hydroxyl group in the molecule, the polymer compound (c) can be reacted. Also, by changing the reaction ratio between the epoxy resin and the unsaturated monobasic acid, the epoxy group can be left in the molecule, or when the hydroxyl group in the vinyl ester resin is modified with an acid anhydride, the carboxyl group is included in the molecule. Can be left to react the polymer compound (c). Alternatively, first, a polymer compound (c) can be reacted with the epoxy resin.

Examples of the epoxy resin include glycidyl ethers of polyhydric phenols such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, and brominated epoxy resin, and dipropylene. Glycidyl ethers of polyhydric alcohols such as glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and diglycidyl ether of an alkylene oxide adduct of bisphenol A, 3,4-epoxy-6-methylcyclohexylmethyl-3,4- Epoxy-6-methylcyclohexanecarboxylate,
Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl p-
Glycidyl esters such as oxybenzoic acid and glycidyl dimer acid; glycidylamines such as tetraglycidyldiaminodiphenylmethane, tetraglycidyl m-xylylenediamine, triglycidyl P-aminophenol, and N, N-diglycidylaniline;
A heterocyclic epoxy resin such as diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate, 2,2 ′, 4,4′-tetraglycidoxybiphenyl, dimethylbisphenol C diglycidyl ether;
And bisbeta-trifluoromethyldiglycidylbisphenol A. These epoxy resins may be used alone or in combination of two or more.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethylmalate, monopropylmalate, and the like.
Monobutyl malate, mono (2-ethylhexyl) malate, sorbic acid and the like can be mentioned. These acids are used alone or in combination of two or more.

Further, various modified vinyl ester resins described on pages 22 to 31 of "Vinyl Ester Resin" (edited by Research Group of Vinyl Ester Resins, Chemical Daily, 1993) can also be used. For example, a vinyl ester resin of a type in which an acid anhydride such as maleic anhydride or phthalic anhydride or phosphoric acid is added to a hydroxyl group in the vinyl ester resin.

The vinyl urethane resin is an oligomer obtained from a polyol compound, an organic polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate. The vinyl urethane resin can leave the isocyanate group in the molecule by changing the reaction ratio of the above reactants, so that the polymer compound (c) can be reacted. Or,
First, there is a method of reacting a polymer compound (c) with a polyol compound.

The polyol compound is a general term for a compound having a plurality of hydroxyl groups in a molecule. In place of the hydroxyl group, a functional group having an active hydrogen capable of reacting with an isocyanate group, such as a carboxyl group, an amino group or a mercapto group, is used. Compounds may be used. Such polyol compounds include, for example, polyester polyols, polyether polyols, acrylic polyols, polycarbonate polyols, polyolefin polyols, castor oil polyols, caprolactone-based polyols and the like, each of which is used alone or in combination of two or more. As the organic polyisocyanate compound, those described above can be used.

The acrylic resin is a thermoplastic acrylic polymer derived from (meth) acrylate and a polymerizable unsaturated monomer having (meth) acrylate as a main component. An acrylic resin composition is composed of an unsaturated monomer. (Meta)
An acrylic acid ester is an essential component, and if necessary, another polymerizable unsaturated monomer copolymerizable with the (meth) acrylic acid ester is used in combination, and the monomer mixture is polymerized. . When an acrylic resin is used, it is necessary to select an acrylic resin having a functional group capable of reacting with a functional group derived from the compound (B) of the polymer compound (c).

Since the acrylic resin is used in the form of a syrup dissolved in a polymerizable unsaturated monomer such as the (meth) acrylic acid ester, the acrylic resin preferably has a molecular weight of 100,000 or less. And the like, and can be obtained by a general polymerization method. In addition, a syrup obtained by prepolymerizing the monomer at 10 to 40% by weight can be used as it is.

The amount of the polymer compound (c) used is preferably 0.01 to 20 parts by weight, more preferably 100 parts by weight of the radical copolymerizable unsaturated resin composition. 0.1 to 10 parts by weight. Within this range, an appropriate addition amount may be selected depending on the purpose and the type of the radical copolymerizable unsaturated resin (a). When the addition amount is small, the amount of the polymer substance (d), which is a reaction product of the precursor polymer compound (c) and the resin (a), is small, and the compound (b) and the resin (a) Sufficient compatibility cannot be obtained. As the amount of addition increases, the amount of the polymer substance (d) increases, so that the compatibilizing effect increases. However, when the amount exceeds a certain amount, the compatibilizing effect does not change much. Further, when the number of functional groups of the polymer compound (c) is 2 or more, if the amount of the polymer compound (c) added is large, the viscosity of the resin composition increases, which may lead to gelation. Here, the amount of the polymer compound (c) added is the amount of the polymer compound (c) added as a solid content excluding the solvent.

The reaction between the radical copolymerizable unsaturated resin (a) and the polymer compound (c) is carried out during, after, and after the synthesis of the radical copolymerizable unsaturated resin (a). It is preferable to carry out by adding the polymer compound (c) to any of the addition and mixing of the monomer (a ′). That is, it is a method of adding it to any one during the period from the preparation of the synthesis in (A) to the removal of the resin composition. In any case, it is important to efficiently react the added polymer compound (c) with the radical copolymerizable unsaturated resin (a).
It is preferable that 0% by weight or more reacts with the radical copolymerizable unsaturated resin (a). It is more preferably at least 90% by weight. For this, the reaction temperature is preferably between 0 and 300
The reaction is carried out at a temperature of preferably 0.1 to 5 hours. In particular, it is more preferable to add the polymer compound (c) after the completion of the synthesis of the resin (a) and react at a reaction temperature of 60 to 220 ° C. The amount of the polymer compound (c) added is preferably 0.005 to 10 parts by weight based on 100 parts by weight (solid content) of the radical copolymerizable unsaturated resin (a).

The above is a radical copolymerizable unsaturated resin composition in which a polymer compound (c) is added in a specific amount to the radical copolymerizable unsaturated resin composition to partially form the polymer substance (d). Was a method of producing a polymer compound (c)
Is added to the radical copolymerizable unsaturated resin (a) in an amount equal to or greater than the solid content of the radical copolymerizable unsaturated resin (a).
To a polymeric substance (d) to produce a compatibilizer,
It can be used by adding it to another radical copolymerizable unsaturated resin composition, preferably in an amount of 0.01 to 20 parts by weight. Of course, by mixing the above-mentioned partially copolymerizable radically polymerizable unsaturated resin composition with a polymer material (d) with another radically copolymerizable unsaturated resin composition, a resin composition having good compatibility can be obtained. You can also.

By such a reaction operation, the polymer (d) obtained by the reaction between the radical copolymerizable unsaturated resin (a) and the polymer compound (c) is added to the radical copolymerizable unsaturated resin composition. It is important that the generation exists. Since the polymer substance (d) has both a polymer block mainly composed of styrene and a radical copolymerizable unsaturated resin block in one molecule, the radical copolymerizable unsaturated resin (a) and the compound (b) Can effectively work as a compatibilizer. The number average molecular weight of the polymer substance (d) is preferably 2,000 to 100,000.

The radical copolymerizable resin composition of the present invention comprises a radical copolymerizable unsaturated resin (a) and a polymerizable unsaturated monomer (a '), and comprises a compound (b) and a polymer substance. (D) is included as an essential component, and if necessary, additives such as a polymerization inhibitor, a curing catalyst, an internal release agent, and a pigment are added. A filler and a reinforcing material may be further added to the resin composition.

The molding material of the present invention comprises a radical copolymerizable resin composition, a curing catalyst, and a fiber reinforcing material, to which additives such as a filler, a curing catalyst, an internal mold release agent, and a pigment are added as required. It is.

As the polymerizable unsaturated monomer (a ′), aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene and chlorostyrene, and (meth) acrylates are used. Also, is a functional monomer,
Hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate;
Monomers having a carboxyl group such as (meth) acrylic acid can also be used. Further, other unsaturated esters such as vinyl acetate and vinyl propionate, vinyl halide monomers such as vinyl chloride and vinylidene chloride, and unsaturated nitriles such as acrylonitrile and methacrylonitrile can be used in combination.

Radical copolymerizable unsaturated resin (a), that is,
The amount of the polymerizable unsaturated monomer (a ') to be added to the unsaturated polyester, vinyl ester resin, vinyl urethane resin or acrylic resin is not particularly limited, but is in the range of 10% by weight to 70% by weight. Is preferred, and 20
More preferably, it is in the range of 50% by weight to 50% by weight.

The polymerization inhibitor is added at the time of production or after the reaction to prevent gelation due to polymerization and to adjust the storage stability or curability of the resulting radical copolymerizable resin composition. . The polymerization inhibitor is not particularly limited, and a conventionally known polymerization inhibitor can be used. Specific examples include hydroquinone, methylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, copper chloride and the like. One of these polymerization inhibitors may be used alone, or two or more thereof may be used by mixing them at appropriate times. still,
The addition amount of the polymerization inhibitor is not particularly limited, but is preferably 0.001 to 1% by weight in the resin composition.
It is.

As the curing catalyst, a known high-temperature curing type or room-temperature curing type catalyst can be used. Examples of the high temperature curing type catalyst include methyl ethyl ketone peroxide, t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, di-t-butyl peroxy-3,3,5-trimethylcyclohexane, t- Organic peroxides such as butyl peroxybenzoate, dicumyl peroxide, and t-butyl hydroperoxide can be used. These curing catalysts are used alone or in combination of two or more.

Examples of the room temperature curing catalyst include a curing system obtained by using a metal salt such as cobalt naphthenate or cobalt octenoate in combination with a ketone peroxide such as methyl ethyl ketone peroxide or methyl isobutyl ketone peroxide. Aromatic 3 such as N, N-dimethylaniline
A redox catalyst system using a combination of a secondary amine and an acyl peroxide such as benzoyl peroxide can be used.

Examples of the filler include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barite, baryta, silica, silica sand, dolomite limestone,
Gypsum, aluminum fine powder, hollow balloon, alumina, glass powder, aluminum hydroxide, hydrated water, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide and the like can be mentioned. These fillers are selected in consideration of workability, strength, appearance, economy, and the like of the obtained molded product, but usually, calcium carbonate, aluminum hydroxide, silica, talc, and the like are often used. Surface-treated ones may be used.

As the reinforcing material, those usually used as a fiber reinforcing material may be used, and examples thereof include glass fiber, polyester fiber, phenol fiber, polyvinyl alcohol fiber, aromatic polyamide fiber, nylon fiber, and carbon fiber. Examples of these forms include chopped strands, chopped strand mats, rovings, and woven fabrics. These fiber reinforcing materials are selected in consideration of the viscosity of the composition, the strength of the obtained molded article, and the like.

Examples of the internal release agent include higher fatty acids such as stearic acid, higher fatty acid salts such as zinc stearate, and alkyl phosphates.

Further, a sheet molding compound (hereinafter abbreviated as SMC), a bulk molding compound
When preparing a molding material such as a compound (hereinafter abbreviated as BMC), a metal oxide or hydroxide such as magnesium oxide or calcium hydroxide can be added as a thickener.

The viscosity reducing agent is added for the purpose of reducing the viscosity and improving the workability, and is not particularly limited as long as it reduces the viscosity of the resin composition.

In the present invention, the low-shrinkage imparting compound (b) to be mixed with the radical copolymerizable unsaturated resin composition for the main purpose of reducing the shrinkage is not particularly limited. Polystyrene, a copolymer of styrene and a polymerizable unsaturated monomer, a styrene-conjugated diene block copolymer, a styrene-hydrogenated conjugated diene block copolymer, a double bond in these polymers, and other compounds Can be used. The copolymer of styrene and a polymerizable unsaturated monomer is obtained by polymerizing styrene and one or more polymerizable unsaturated monomers selected from the aforementioned polymerizable unsaturated monomers. If it is a copolymer, its polymerization method and structure of the copolymer are not particularly limited. A styrene-conjugated diene-based block copolymer is a block copolymer composed of a styrene component and a conjugated diene component obtained by polymerizing styrene and a conjugated diene. Butadiene, isoprene, 1,3-
Pentadiene or the like is used. Further, a styrene-hydrogenated conjugated diene block copolymer obtained by hydrogenating the styrene-conjugated diene block copolymer may be used. The structural unit of the block copolymer is not particularly limited, and includes a repeating unit of styrene and conjugated diene such as styrene-conjugated diene, styrene-conjugated diene-styrene, and conjugated diene-styrene-conjugated diene.

Further, a thermoplastic acrylic resin polymer, a vinyl acetate polymer, and a saturated polyester derived from a polymerizable unsaturated monomer having (meth) acrylate and (meth) acrylate as main components are also used. be able to.

The radical copolymerizable resin composition of the present invention comprises
The present invention can be applied to all applications where a radical copolymerizable resin composition has been used. For example, the molding material (S
Press molding and injection molding as MC and BMC, spray molding, hand lay-up molding, casting, pultrusion molding, resin transfer molding, metal matched die molding, etc.), coating material (paint, putty, decorative board, sealing material, lining) Material).

The molded article of the present invention includes living equipment such as bathtubs, kitchen counters, vanities, waterproof pans, resin concrete, tanks, septic tanks, artificial marble, panels,
Civil engineering building materials such as corrugated sheets and pipes; automotive parts such as cylinder head covers and headlamp reflectors; electric parts such as motor seals and breakers; boats, ships and other ships; No.

[0054]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Further, “parts” in the text indicates parts by weight.

Example 1 (Synthesis of polymer compound (c)) In a 1-liter four-necked flask equipped with a nitrogen inlet tube, 306 g of styrene was synthesized using an azo-based initiator as the styrene-based polymer (A). 300 g of polystyrene having a number average molecular weight of 9600 and having one hydroxyl group at one end was charged with 0.2 g of hydroquinone, and heated to 70 ° C. in a nitrogen stream. Next, 0.3 g of dibutyltin laurate and 5.5 g of tolylene diisocyanate as the compound (B) were added and reacted at 70 ° C. for 2 hours to obtain a polymer compound (c).
This is designated as polymer compound (c-1). Cool this,
A polymer compound (c-1) styrene solution having a solid content of 50% was obtained. This is designated as polymer compound solution A. The polymer compound (C-1) thus obtained was capped with dibutylamine, and the number average molecular weight measured by gel permeation chromatography was 11,000.

Example 2 (Synthesis of Polymer Compound (C)) In a one-liter four-necked flask equipped with a nitrogen inlet tube, 318 g of styrene and a styrene polymer (A) having two hydroxyl groups at one end as a styrene polymer (A). 300 g of polystyrene having a number average molecular weight of 6000 (macromonomer HS-6: manufactured by Toagosei Co., Ltd.) and 0.2 g of hydroquinone were charged and heated to 70 ° C. in a nitrogen stream. Next, 0.3 g of dibutyltin laurate and 18 g of tolylene diisocyanate as the compound (B) were added and reacted at 70 ° C. for 2 hours to obtain a polymer compound (c). This is referred to as a polymer compound (C-2).
This was cooled and a polymer compound having a solid content of 50% (C-2)
A styrene solution was obtained. This is designated as polymer compound solution B. The number average molecular weight measured after the thus obtained polymer compound (c-2) was capped with dibutylamine was 7,000.

Example 3 (Synthesis of Radical Copolymerizable Resin Composition) 390 g of propylene glycol and 470 g of maleic anhydride were charged into a two-liter four-necked flask equipped with a nitrogen inlet tube, and heated to 210 ° C. in a nitrogen stream. The reaction was completed by stirring for about 9 hours while maintaining the reaction temperature to obtain an unsaturated polyester resin. The acid value of this unsaturated polyester resin was 19 mgKOH / g. Thereafter, after adding 0.4 g of hydroquinone, 150 g of styrene was added, and the mixture was cooled to 90 ° C. Next, the polymer compound solution A
Was added and reacted at 90 ° C. for 3 hours. Next, 280 g of styrene was added and the mixture was cooled to obtain an unsaturated polyester resin composition A (hereinafter referred to as unsaturated polyester resin A).

Example 4 (Synthesis of Radical Copolymerizable Resin Composition) An unsaturated polyester resin composition was prepared in the same manner as in Example 3 except that the polymer compound solution B was used instead of the polymer compound solution A. A product B (hereinafter referred to as unsaturated polyester resin B) was obtained.

Example 5 (Synthesis of Radical Copolymerizable Resin Composition) 160 g of propylene glycol, 220 g of neopentyl glycol and 430 g of maleic anhydride were charged into a two-liter four-necked flask equipped with nitrogen and air inlet tubes. After the temperature was raised to 150 ° C, the temperature was cooled to 120 ° C, 175 g of dicyclopentadiene was charged, and the reaction was carried out at a temperature of 120 to 140 ° C until the acid value became 220 mgKOH / g. Next, 0.5 g of hydroquinone was added and reacted for 6 hours to obtain an unsaturated polyester resin. The acid value of this unsaturated polyester was 18 mgKOH / g. Here, styrene 1
80 g was added and cooled to 90 ° C. Next, 23 g of the polymer compound solution A was added and reacted for 3 hours. Next, 350 g of styrene was added and the mixture was cooled to obtain an unsaturated polyester resin composition C (hereinafter, referred to as unsaturated polyester resin C).

Example 6 (Synthesis of Radical Copolymerizable Resin Composition) In a 2 liter four-necked flask equipped with nitrogen and air inlet tubes, 1000 g of bisphenol A type epoxy resin (epoxy equivalent 410), 210 g of methacrylic acid, 0.5 g of hydroquinone was charged, and the temperature was raised to 90 ° C. under a gas flow in which nitrogen and air were mixed at a ratio of 1: 1. Here 2-
2.5 g of methyl imidazole was added, the temperature was raised to 105 ° C., and the mixture was reacted for 10 hours to obtain a vinyl ester resin. The acid value of this vinyl ester was 6 mgKOH / g. After cooling to 90 ° C., 220 g of styrene and 0.1 ml of toluhydroquinone were added.
8 g and 26 g of the polymer compound solution A were added and reacted at 90 ° C. for 3 hours. Next, 300 g of styrene was added and the mixture was cooled to obtain a vinyl ester resin composition A (hereinafter, referred to as vinyl ester resin A).

Example 7 (Synthesis of Radical Copolymerizable Resin Composition) In a 2-liter four-necked flask equipped with nitrogen and air inlet tubes, 1000 g of bisphenol A type epoxy resin (epoxy equivalent: 410) and 210 g of methacrylic acid were added. And 0.5 g of hydroquinone, and the temperature was raised to 90 ° C. under a gas flow in which nitrogen and air were mixed at a ratio of 1: 1. Here 2
2.5 g of -methylimidazole was added, and the mixture was heated to 105 ° C and reacted for 10 hours to obtain a vinyl ester resin. The acid value of this vinyl ester was 6 mgKOH / g. 0.8 g of toluhydroquinone and 260 g of styrene were added thereto, cooled to 90 ° C., 100 g of maleic anhydride was added, and the mixture was further reacted for 3 hours. 28 g of the polymer compound solution A was added thereto and reacted at 90 ° C. for 3 hours. Next, 300 g of styrene was added and the mixture was cooled to obtain a vinyl ester resin composition B (hereinafter, referred to as vinyl ester resin B).

Example 8 (Synthesis of Radical Copolymerizable Resin Composition) A novolak type epoxy resin (epoxy equivalent: 1) was placed in a two-liter four-necked flask equipped with nitrogen and air introduction tubes.
82) 800 g, 376 g of methacrylic acid and 0.4 g of hydroquinone were charged, and the temperature was raised to 90 ° C. under a gas flow in which nitrogen and air were mixed at a ratio of 1: 1. 2.4 g of 2-methylimidazole was added thereto, and the temperature was raised to 105 ° C.
The reaction was carried out for an hour to obtain a vinyl ester resin. The acid value of this vinyl ester was 7 mgKOH / g. To this, 1 g of toluhydroquinone and 210 g of styrene were added, and the mixture was cooled to 90 ° C., and 172 g of maleic anhydride was added and reacted for 3 hours. 29 g of the polymer compound solution A was added thereto, and 90 ° C.
For a further 3 hours. Here, styrene (370 g) was added and cooled to obtain a vinyl ester resin composition C (hereinafter, referred to as vinyl ester resin C).

Comparative Example 1 (Synthesis of Radical Copolymerizable Resin Composition) Synthesis was performed in the same manner as in Example 3 except that the polymer compound solution A was not used. The unsaturated polyester resin composition D
(Hereinafter referred to as unsaturated polyester resin D).

Comparative Example 2 (Synthesis of Radical Copolymerizable Resin Composition) Synthesis was performed in the same manner as in Example 5 except that the polymer compound solution A was not used. This was used as an unsaturated polyester resin composition E
(Hereinafter referred to as unsaturated polyester resin E).

Comparative Example 3 (Synthesis of Radical Copolymerizable Resin Composition) Synthesis was carried out in the same manner as in Example 6 except that the polymer compound solution A was not used. This is designated as vinyl ester resin composition D (hereinafter, referred to as vinyl ester resin D).

Comparative Example 4 (Synthesis of Radical Copolymerizable Resin Composition) Synthesis was performed in the same manner as in Example 7 except that the polymer compound solution A was not used. This is referred to as a vinyl ester resin composition E (hereinafter, referred to as vinyl ester resin E).

Comparative Example 5 (Synthesis of Radical Copolymerizable Resin Composition) Synthesis was performed in the same manner as in Example 8 except that the polymer compound solution A was not used. This is designated as vinyl ester resin composition F (hereinafter, referred to as vinyl ester resin F).

Example 9 40 g of a 50% styrene monomer solution of polystyrene having a weight average molecular weight of 280,000 was added to 160 g of the unsaturated polyester resin A, and the mixture was sufficiently stirred and mixed. Table 1 shows the result of visually observing the time until the separation of the low-shrinkage agent at that time.

Examples 10 to 14 The same procedures as in Example 9 were carried out except that unsaturated polyester resins B and C and vinyl ester resins A to C were used instead of the unsaturated polyester resin A. The results are shown in Table 1.

[0070]

[Table 1]

(Evaluation method) Time to separation: After stirring and mixing the resin composition, the mixture was placed in a 240 cc glass bottle,
It was left in a room kept at 3 ° C. Immediately after mixing, a uniformly cloudy resin composition was obtained in each case. The time at which the separation of the low-shrinkage agent became observable at the top of the liquid was defined as the time until separation. If no separation was observed after one month, "No separation" was described.

Comparative Examples 7 to 11 The same procedures as in Example 9 were carried out except that unsaturated polyester resins D and E and vinyl ester resins DF were used instead of the unsaturated polyester resin A. The results are shown in Table 2.

Comparative Example 12 157 g of unsaturated polyester resin D, 3 g of a 50% styrene solution of Modiper S501 (manufactured by NOF Corporation) as a compatibilizer, and 5 g of polystyrene having a weight average molecular weight of 280,000
40 g of a 0% styrene monomer solution was added, followed by sufficient stirring and mixing. Table 2 shows the result of visually observing the time until the separation of the low-shrinkage agent at that time.

[0074]

[Table 2]

Example 15 To 160 g of the unsaturated polyester resin A, 40 g of a 50% styrene monomer solution of KRATON D-1101 (manufactured by Shell Japan Co., Ltd.) as a styrene butadiene rubber was added, and the mixture was sufficiently stirred and mixed. Table 3 shows the result of visually observing the time until the separation of the low-shrinkage agent at that time.

Examples 16 to 20 The same procedures as in Example 15 were carried out except that unsaturated polyester resins B and C and vinyl ester resins A to C were used instead of the unsaturated polyester resin A. The results are shown in Table 3.

[0077]

[Table 3]

Comparative Examples 13 to 17 The same procedures as in Example 15 were carried out except that unsaturated polyester resins D and E and vinyl ester resins DF were used instead of the unsaturated polyester resin A. The results are shown in Table 4.

Comparative Example 18 157 g of unsaturated polyester resin D, 3 g of a 50% styrene solution as a compatibilizer, and KRATON D-1101 (Shell Japan Co., Ltd.) as styrene butadiene rubber
40 g of a 50% styrene solution was added, and the mixture was sufficiently stirred and mixed. Table 4 shows the result of visually observing the time until the separation of the low-shrinkage agent at that time.

[0080]

[Table 4]

Example 21 80 parts of unsaturated polyester resin A, 0.06 part of parabenzoquinone, and polystyrene 5 having a weight average molecular weight of 280,000
20 parts of 0% styrene monomer solution, zinc stearate 4
Parts, calcium carbonate 140 parts, pigment (Polyton Gray P
T-8809, manufactured by Dainippon Ink and Chemicals, Inc.), 1 part of t-butyl perbenzoate as a curing catalyst was mixed,
The mixture was sufficiently stirred until it was uniformly dispersed. Thereafter, 1.3 parts of magnesium oxide as a thickener was further added to the mixture, and the fiber length as a reinforcing material was adjusted so that the content in the obtained unsaturated polyester resin composition was 25% by weight. One-inch glass fibers were dispersed, and SMC was prepared using a conventional SMC manufacturing apparatus. The obtained SMC was wrapped in an aluminum evaporated film and aged at 40 ° C. for about 24 hours.
Thereafter, the SMC is supplied to a mold adjusted to an upper mold of 145 ° C. and a lower mold of 135 ° C., and is pressed and maintained at a pressure of 70 kgf / cm ² (surface pressure) for 4 minutes, thereby obtaining a flat plate of 30 × 30 cm and a thickness of 3 mm. Molded. Evaluation of scumming, uniform coloring, surface smoothness, and gloss of the obtained molded product was performed by the following methods. Table 5 shows the results.

Examples 22 to 26 The same evaluation as in Example 21 was carried out except that unsaturated polyester resins B and C and vinyl ester resins A to C were used instead of the unsaturated polyester resin A. Table 5 shows the results.

[0083]

[Table 5]

(Evaluation Method) Evaluation of Scumming: The presence or absence of scumming is visually determined. Evaluation of uniform coloring property: Along with visual evaluation, a color difference meter (Color Machine # 80 manufactured by Nippon Denshoku Industries Co., Ltd.) is used to measure L values at 12 or more points at 1 cm intervals on an arbitrary straight line of the molded product. The average value of the L values is calculated, and the variation (standard deviation) of the L values is calculated using the average value as an index. Evaluation of surface smoothness: visual evaluation and surface distortion measuring machine SURFMATIC
(Tokyo Boeki Co., Ltd.) is used to measure the second derivative of the surface irregularities. Surface gloss: Visual and gloss meter (Murakami Color Research Laboratory: G
M26D) and evaluated by 60 ° gloss.

(Evaluation Criteria): Good ◎> ○> △> × Poor Uniform Colorability: ＝= No color unevenness is observed at all, and the variation (standard deviation) of L value is 0.5 or less. ＝= Although little color unevenness can be visually confirmed, the variation (standard deviation) of the L value is 0.7 or less. Δ: Color unevenness can be visually confirmed, and the variation of L value (standard deviation) is larger than 0.7 and smaller than 1.0. × = Evident color unevenness can be visually confirmed, and the variation (standard deviation) of the L value is 1.0 or more.

Surface smoothness: ＝= second derivative is 500 or less. ＝= Secondary derivative is 700 or less. Δ = Secondary differential coefficient is greater than 700 and less than 1000. X = Second derivative: 1000 or more.

Surface gloss: ＝= gloss at 60 ° is 90 or more. ＝= Gloss at 60 ° is 85 or more. Δ = 60 ° gloss is 80 or more and less than 85. X = Gloss at 60 ° is less than 80.

Comparative Examples 19 to 23 Evaluations were made in the same manner as in Example 21 except that unsaturated polyester resins D and E and vinyl ester resins DF were used instead of the unsaturated polyester resin A. The results are shown in Table 6.

[0089]

[Table 6]

As is clear from the results shown in Tables 1 and 3, in all of Examples 9 to 20 which satisfied the conditions of the present invention, a high compatibilizing effect was obtained with the polymer (d), and one month after mixing. In some cases, no separation of the low-shrinkage agent component in the composition occurred even after the lapse of time. On the other hand, Tables 2 and 4
In Comparative Examples 7 to 18 described in (1) and (2), the sufficient compatibilizing effect could not be obtained because the conditions of the present invention were not satisfied. In each case, separation occurred after several minutes to two days.

As is clear from the results shown in Table 5, Examples 21 to 26 all satisfy the conditions of the present invention. It was possible to obtain a molded article which was free from scumming and had excellent uniform coloring, surface smoothness and surface gloss, in which molding defects due to the separation of the shrinkage agent were improved. On the other hand, Comparative Examples 19 to 24 described in Table 6 did not satisfy the requirements of the present invention, and were molded articles in which molding defects occurred due to the separation of the low-shrinkage agent.

[0092]

The polymer compound (c) of the present invention is a polymer compound which improves the compatibility between the radically copolymerizable unsaturated resin (a) and the polymer containing polystyrene as a main component used as a low-shrinking agent. A precursor compound that produces a molecular substance (d), which is a radical copolymerizable unsaturated resin that can solve storage and molding problems caused by poor compatibility. It can be provided by reacting with (a). The polymer compound (C) of the present invention is added after the synthesis at the time of synthesizing the radical copolymerizable unsaturated resin (A), and acts as a compatibilizer by reacting with the radical copolymerizable unsaturated resin (A). A polymer substance (d) can be obtained. The polymer (d) alone may be produced and added to the radically polymerizable unsaturated resin composition, or the polymer (c) may be added to the radically copolymerizable unsaturated resin composition to partially Specifically, the polymer substance (d) can be contained to enable one-package of a mixture of the low-shrinkage agent and the radically polymerizable resin composition, thereby providing a means for achieving high added value of a molded product. By such a radical copolymerizable unsaturated resin composition, it is possible to provide a molding material and a molded article capable of obtaining a molded article having no scumming and excellent in uniform coloring property, surface smoothness and surface gloss.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (reference) // C08L 101: 00 C08L 101: 00 F term (reference) 4F071 AA22 AA42 AA49 AA53 AF53 AH03 AH12 BA02 BB05 BB03 BB05 BC03 BC04 BC05 BC06 4J027 AB02 AE02 AG01 BA04 BA05 BA06 BA07 BA08 BA13 CA04 CA10 CD02 4J031 AA13 AA47 AA50 AA56 AB01 AC08 AD01 AF05 AF12 AF13 AF17 AF19 AF23 4J100 BA38H CA31 HA35 HA61 HC51 JA01 JA05 JA43 JA57 JA67

Claims (12)

[Claims] 1. A radical copolymerizable unsaturated resin composition comprising a radically copolymerizable unsaturated resin (a) and a polymerizable unsaturated monomer (a ′) and a low shrinkage with the unsaturated resin (a). A polymer compound (c) which is a precursor for producing a polymer substance (d) having an action of making the compound (b) compatible with the compound (b) added for the main purpose of chemical conversion,
(A) a styrene-based polymer having polystyrene as a main component and having one or more functional groups in the molecule; and (B) a styrene polymer having two or more functional groups in the molecule and at least one of the functional groups. A compound having a functional group capable of reacting with a functional group of the styrenic polymer (A), wherein the polymer compound (c) has at least a functional group derived from the compound (B). A polymer compound (c), wherein one is left. 2. The functional group of the styrenic polymer (A) is at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group, an amino group, and a mercapto group. The polymer compound described in (c). 3. The polymer compound according to claim 1, wherein at least one of the functional groups of the styrenic polymer (A) is located at a molecular terminal of the polymer. 4. The styrenic polymer (A) has a functional group number of:
The polymer compound (C) according to any one of claims 1 to 2, wherein the polymer compound is 1 to 4. 5. The polymer compound (c) according to claim 1, wherein the styrene polymer (A) has a number average molecular weight of 1,000 to 50,000. 6. The polymer compound (c) according to claim 1, wherein the compound (B) is an organic polyisocyanate compound. 7. The polymer compound (C) is mainly a compound having the structure of (A)-(B) when the polymer (A) has one functional group, and the functional group of the polymer (A) is Two cases (B)
The polymer compound according to any one of claims 1 to 6, which is a compound having a structure of-(A)-(B). 8. The polymer according to any one of claims 1 to 7, wherein the average number of functional groups derived from the compound (B) remaining per molecule of the polymer compound (c) is 1 to 4. Compound (c). 9. A radical copolymerizable unsaturated resin (a) having a functional group capable of reacting with the functional group of the compound (B) in the molecule, and a radical copolymerizable unsaturated monomer (a ′). 9. The polymerizable unsaturated resin composition, wherein the polymer compound (c) according to any one of claims 1 to 8 is added, and the radical copolymerizable unsaturated resin is added to the radical copolymerizable unsaturated resin composition. A radical copolymerizable unsaturated resin composition comprising a polymer substance (d) obtained by reacting (a) with a polymer compound (c). 10. A polymerizable unsaturated monomer (a ′) during or after the synthesis of the radical copolymerizable unsaturated resin (a), or after the synthesis of the radical copolymerizable unsaturated resin (a).
A method for producing a radical copolymerizable resin composition, comprising adding the polymer compound (C) according to any one of claims 1 to 8 after the addition and reacting. 11. A molding material comprising the radical copolymerizable resin composition according to claim 9. 12. A molded article using the radical copolymerizable resin composition according to claim 9 or the molding material according to claim 11.